Patent GB-577735-A (GB)
Title: New and useful materials derived from ethylene urea
Filed: 1944-11-23
Abstract: Compounds of the general formula <FORM:0577735/IV/1> or <FORM:0577735/IV/2> where R and R1 which may be the same or different, are hydrogen or monovalent aliphatic hydrocarbon radicals which may be saturated or unsaturated, acyclic or cyclic, unsubstituted or substituted by inert groups such as alkoxy, thioether or aryl groups; are prepared by reacting ethylene urea with formaldehyde, preferably in the presence of a basic catalyst such as sodium, potassium, barium or calcium hydroxides or an organic base such as triethylamine or pyridine.  The hydroxy compound may be thereafter etherified by reacting with an alcohol in the presence of an acidic catalyst such as hydrochloric, sulphuric, phosphoric, formic or citric acids, sodium acid sulphate or sodium acid phosphate.  In the examples: (1) paraformaldehyde and sodium hydroxide dissolved in methanol are added to a warm methanol solution of ethyleneurea.  On cooling, a precipitate of N : N1-bis-(hydroxymethyl) ethylene urea is obtained; (2) a mixture of ethylene urea, formaldehyde and water is agitated at room temperature.  After standing, a product is obtained containing an ethylene urea: formaldehyde molal ratio of 1 : 1; (3) the process of example (1) is repeated but on cooling, the solution is made acid with a methanol solution of hydrochloric acid.  After standing, the solution is neutralized and distilled under reduced pressure yielding N : N1-bis-(methoxymethyl) ethyleneurea; (4) the process of example (3) is repeated using butanol in place of methanol.  Other alcohols which may be used to prepare the N-alkoxymethyl ethyleneureas are stated to be ethyl, propyl, isopropyl, isobutyl, tertiary butyl, octyl, dodecyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, butoxyethyl, benzyl, allyl and cyclohexyl alcohols.  The chain of carbon atoms in the alcohol may be interrupted by other atoms such as oxygen or sulphur.  The products of the invention may be used as modifying agents for polymeric materials containing hydroxyl groups, giving improved resistance to organic solvents and increased softening points.  Cellulose, cellulose acetate, ethylcellulose, polyvinylalcohol, polyvinyl butyrol resins, hydroxylated rubber and alkyd resins may be treated in this way. Natural or artificial cellulosic fibres are rendered crease resistant, waterproof and more receptive to dyes by treatment with the products of the invention.  They may also be used as ingredients of brake fluid compositions, as oxidation inhibitors and as intermediates in the preparation of N : N1-dimethylethylenediamine by hydrogenation and hydrolysis. They can be used as plasticisers for cellulose esters such as cellulose acetate and as softeners for cellophane.  Water soluble resins are obtained by dehydrating aqueous solutions of the hydroxymethyl derivatives of ethylene urea under alkaline conditions and heating the residue.  When the resin obtained from N-bis-hydroxymethyl ethyleneurea by dehydration under vacuum is heated with urea a clear fluid is obtained.  The mono- or bis-hydroxymethylethyleneureas yield viscous syrups on heating with urea or dimethylol urea in aqueous alkaline solution which on acidification and heating yield resins.  A moulding powder is obtained by impregnating cellulose pulp with an aqueous solution of N-bis-hydroxymethyl ethyleneurea which may be compression moulded. The products of the invention may be employed in the impregnation of wood or other substances.  Specification 571,727 is referred to.  The Specification as open to inspection under Sect. 91 states that ethylene thiourea may be used in place of ethylene urea in the process of the invention and gives an example in which ethylene urea is prepared by heating together urea and ethylene diamine. This subject-matter does not appear in the Specification as accepted.ALSO:Compounds of the general formula <FORM:0577735/V/1> or <FORM:0577735/V/2> where R and R1 which may be the same or different, are hydrogen or monovalent aliphatic hydrocarbon radicals which may be saturated or unsaturated, acyclic or cyclic, unsubstituted or substituted by inert groups such as alkoxy, thioether or aryl groups; are stated to react with hydroxylated rubber to give a product having improved resistance to organic solvents and an increased softening point.  Specification 571,727, [Group IV], is referred to.  The Specification as open to inspection under Sect. 91 states that the corresponding ethylene thiourea derivatives may be employed likewise. This subject-matter does not appear in the Specification as accepted.